US5939192A - Moulding made from or including an environmentally acceptable material, a process for manufacturing the same, and the use of said moulding - Google Patents
Moulding made from or including an environmentally acceptable material, a process for manufacturing the same, and the use of said moulding Download PDFInfo
- Publication number
- US5939192A US5939192A US08/586,902 US58690296A US5939192A US 5939192 A US5939192 A US 5939192A US 58690296 A US58690296 A US 58690296A US 5939192 A US5939192 A US 5939192A
- Authority
- US
- United States
- Prior art keywords
- molding
- group
- fiber material
- plant fiber
- resin acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2938—Coating on discrete and individual rods, strands or filaments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present invention relates to a novel, bio-degradable molding based on plant fiber materials that are integrated into a matrix of at least one biogenic material that has been reduced at high temperature and pressure to a molten state and which has undergone thermoplastic treatment.
- a large number of synthetic materials, filled in part with natural fiber materials, are known for the most varied purposes, particularly for accessory parts, elements of furniture of all kinds and for the most varied branches and areas of industry; these suffer from a severe disadvantage in that they are difficult to dispose of in an environmentally benign manner and are not biologically degradable, at least over the long term and for the most part.
- a material that is based on a plant-fibre material, in particular wood that is integrated into a starch matrix or an appropriately molten biomaterial, the matrix itself incorporating a large number of pores as a result of the expansion that takes place when the starch-fibre material is extruded.
- the solution to this problem is a molding of the type described in the introduction hereto, that is essentially such that it displays the following characteristic features:
- these particles are embedded in a matrix of at least one binding agent that forms a gel-melt, from the group of biopolymers, preferably starches, proteins, lignins, hemi-celluloses, dextrins, pectins and/or chitins, in particular cereals that contain the starches or starch in a predominant quantity, mixed with protein where this is appropriate;
- the total water content of the molding is at most 18%-wt, preferably three-16%-wt, in particular 4-12%-wt, and the underlying molding material contains the following components that are combined up as follows:
- resin acid(s) are understood to be resin acids such as occur when processing natural resins, as well as resin acid derivatives and modified resin acids, e.g., those esterified with polyoles, for example on the basis of diterpenes and/or triterpenes, or the like.
- these also include natural hard resins, soft resins (balsams) and/or gum resins, which containresin acids of this kind as the principal components, for example Dammar resin, copals, elemi, gutti, and the like.
- the new material is characterized by a great similarity to wood.
- This similarity to wood make it amenable to all the known and trusted processes that are familiar in the domain of wood processing, wood finishing, surface treatment and wood joining techniques, such as, for example, drilling, sawing, grinding, chipping, cutting, gluing, dowelling, screwing, lacquering, coating, and the like.
- it permits a synergy of quality that cannot be achieved with conventional plastics, for example, those that are based on polyvinyl or alkylene polymers.
- the new product Compared to wood, the new product has the advantage--amongst others--of unrestricted choice of shape and--as a consequence of its homogeneous structure--the advantage that its characteristics are independent of the direction of its fibers, faults, and growth rings.
- it is made up of bio-polymer(s) and particular fiber materials, it is distinguished by much more rapid biological degradability compared to conventional wood.
- the new product is compact and, for all practical purposes free of pores; any expansion or formation of pores is essentially precluded when it is being manufactured. It has been shown that, in order to achieve the advantageous properties of the new molding as described above, the quantity of the gel-melt binder should be kept relatively small compared to the quantity of plant-fibre material, for example wood, that is used.
- a particularly favorable synergistic bonding of the fibre material into a starch/protein-gel matrix is achieved by the (partial) impregnation of the fibers or the wood particles with resin acid (B), for example of tall oil or natural resins, optionally mixed with fatty acids and/or fats/oils/waxes.
- resin acid for example of tall oil or natural resins, optionally mixed with fatty acids and/or fats/oils/waxes.
- tall oil An important component of the tall oil is abietinic acid, which is a resin acid.
- the tall oil also contains quantities of air-hardening oils that make an additional contribution to the ultimate resistance and stability of the new molding, as well as a considerable proportion of fatty acids, in particular oleic acid.
- Natural resins also contain predominantly resin acids, resin alcohols, and their esters, as well as phenols that have the character of a tanning substance, as well as unsaturated compounds, some of which contain oxygen.
- the tannin character appears in the matrix in combination with protein fractions, in particular, and thus contributes to the stability and resistance to water of the molding according to the present invention.
- Bio-polymers such as starches of every kind and the plant parts that contain them, in particular of rice, potatoes, and corn, form the thermoplastic fraction.
- the starches and/or proteins that are present in the molding substance or in the material can be replaced by other bio-polymers such as lignin and/or hemi-celluloses, completely, or by dextrins, pectins, and/or chitins and the like in part, optionally up to 55%-wt, advantageously up to 20%-wt for specific applications.
- Lignins in particular, can make an additional contribution to increased resistance to water, and those of both plant or of animal origin, for example, the remains left after soya bean extraction, gelatins of every kind, and different collagens and the like are suitable as proteins.
- the fibre material can be of any sort as long as it is of plant origin, e.g., cellulose, pulp, batting, paper and cardboard particles, mechanical wood pulp, etc., and preferably wood particles.
- wood is particularly preferred as plant-fibre material; it imparts a light-beige color to the new material, usually without any additives, and this can be varied to a fairly dark brown, depending on the type of wood and the conditions under which it is processed. Maintaining the appropriate water content of the new molding ensures its wood-like characteristics as well as its resistance to moisture.
- pulp or cellulose as well as cotton fibers or the like; these materials result in products with a high level of homogeneity and strength.
- Other fiber materials that can be used are, for example, straw, kapok, jute, etc.
- the stability and strength of the molding according to the present invention can be controlled over a very wide range by varying the length and thickness of the fibre material that is used these can be, for example, 0.05-35 millimeters, preferably 1-5 millimeters in length and 0.05-3 millimeters, preferably 0.1-1.5 millimeters in thickness.
- the longer the fibers the greater the strength.
- the following components or additives, at concentrations from 0.1-1.5-wt, in particular 0.5-3.0%-wt (relative in each instance to the total weight) are suitable for varying the properties of the new moldings with respect to color, feel, lustre, and strength: pigments, organic or inorganic fillers, tannins, softeners, biocides, and curable heat-hardening components, e.g., aldehyde resins.
- tanning agents if there is a protein melt-gel either in the matrix or present as a matrix, there will also be a tanning-like precipitation of the protein. This will result in a change in the properties, namely, increased resistance to quality-degrading influences, for example, losses of visual quality and, in particular, staining.
- Additives such as resins and rubbers, preferably biogenic resins and rubbers, which increase resistance to both water and moisture, provide an advantageous increase in the spectrum of possible uses.
- a useful secondary effect of polyvalent alcohols (polyols) for example of glycerine, which suppresses expansion, is their added effect as softeners.
- the moldings according to the present invention are amenable both to non-cutting types of processing, such as lacquering, coating, or other similar plastic shaping, and to essentially quasi-thermoplastic and simultaneously cutting processes.
- they are free of the disadvantages or shortcomings displayed by thermoplastic materials with reference to adhesion or the plugging of tools such as abrasive papers, saws, files, etc..
- less dust is generated than is the case during cutting type machining when wood or the useful wood materials are being processed.
- the mouldings according to the present invention feel silky to the touch, even after shaping or other processes whereby material is removed, which means that the customer-friendly and good-feeling material will almost certainly be predestined for the economic production of highly stable, wear-resistant toys that pose no threat to health.
- this is effected in a particularly preferred manner in two process stages: an extrusion stage and a dispersal stage for generating pre-mouldings, e.g., in granulate form, and a thermoplastic re-shaping stage, e.g., injection molding, to manufacture the desired mouldings, which are then distinguished, above all, by their homogeneous shape with statistically uniformly divided particles of the fibre material within the matrix, with a gel-smelt like state of the matrix occurring in a transition stage because of high pressure and high temperature in the course of this process.
- a dispersal stage for generating pre-mouldings, e.g., in granulate form
- a thermoplastic re-shaping stage e.g., injection molding
- the first stage in the process prevents any separation of the extremely different components, which could destroy the homogeneity of the end product, and simplifies the charging of the second process stage, e.g., an injection molding machine, to a significant degree.
- the second stage does not have to be charged immediately after the first stage of the process; rather, should it be necessary, this can be done after intermediate storage and/or conditioning (e.g., adjustment of the total moisture content, incorporation of an additive) and/or after transportation of the pre-mouldings.
- thermoplastic shaping in the second process stage also be effected by extrusion or by molding.
- these moldings being in the form of composite bodies, in particular as multi-layer or laminated bodies, the material bond being based on thermo-plastic welding of the flat material that is used.
- the resin-acid component that, surprisingly, has a favorable effect on the wood-like properties of the new material and which can, in part, originate from the very wood particles that are used, it is extremely important for the density of the new product to prevent, completely, the expansion and pore formation that occur during manufacture, in which connection appropriate manufacturing conditions and expansion suppressants can be of specific help.
- constituent substances of the wood when they are used as the fibre material, because of the pressure and temperature some constituent substances of the wood may be either expressed or dissolved out of the wood, when they enter the gel or the gel matrix, where they enhance its quality, in particular its resistance to water, resistance to microorganisms, as well as its mechanical stability.
- constituent substances can be lignins, hemi-celluloses, tannins, fats or oils, pigments, and--in particular--resins.
- a high degree of compactness and freedom from pores can be achieved in a particularly advantageous manner in that, on the one hand, the extrusion of pre-mouldings, for example, a granulate, is carried out in the first stage of the process at temperatures ranging from 70-135 degrees Celsius, in particular from 100-125 degrees Celsius, and at pressures ranging from 20-100 bar, in particular from 25-80 bar and, on the other hand, the injection molding is carried out in the second stage of the process at temperatures from 110-210 degrees Celsius, in particular from 150-180 degrees Celsius, and at pressures ranging from 250-1200 bar, in particular from 400-700 bar.
- pre-mouldings for example, a granulate
- additives that suppress expansion for example, glycerine, glycol, or polyoxyalkylene-glycol
- additives that suppress expansion for example, glycerine, glycol, or polyoxyalkylene-glycol
- these additives can be mixed into the basic substance at a concentration from 0.5-12%-wt, in particular 2-8%-wt, relative in each instance to the total mass.
- starch modifiers in particular etherification and/or esterification components, and/or proteins modifiers, in particular in the form of pH adjustment and tanning agents.
- a particularly effective measure for ensuring freedom from pores is to degas the fibre component itself, in particular if it is wood, for this means that using the two-stage process according to the present invention, this source of gas development is eliminated from the very outset, and it becomes possible to concentrate fully on suppressing expansion of the matrix or the molding substance.
- Such degassing can be carried out, for example, when the plant fibre material is being heated prior to being introduced into the first stage of the process, at temperatures of 170-220 degrees Celsius, in particular of 180-190 degrees Celsius.
- a (molten) liquid component in particular with the oil or fat component, preferably with hardened plant fat or hardening oils
- a natural, modified resin e.g., diethyleneglycol abietinic acid ester
- its properties as a softener that is independent of moisture are an additional advantage. This effect renders the surface quality of the finished mouldings largely independent of specific external influences, such as variations in humidity.
- the new mouldings that are obtained according to the present invention can be used to advantage for the most varied purposes, for example, as elements in motor vehicle, wood, and furniture construction, in particular for rails, decorative mouldings, edges, profiles, screens, knobs, handles, pegs, hooks, joints, strips, connecting and anchoring elements, furniture legs, housings, accessory parts, instrument panels, panelling, toys, fine household effects, packaging material, etc..
- composition of the molding substance for manufacturing the pre-mouldings e.g., granulate
- One hundred kg of long wood shavings, 0.2-5 millimeters long, are thoroughly mixed in a heatable mixer with 5 kg of hardened plant fat at 65 degrees Celsius, so that the wood absorbs the molten-liquid fat completely.
- This dry mixture is placed in an extruder, with the various liquids or liquid phases being metered in at different locations on the extruder housing.
- the resin acid components (Sacocell 309 is a derivative of abietinic acid), emulsified in water and with a solids content of 50%-wt, is introduced shortly after the entry point; the glycerine is introduced at the middle, and the linseed oil is introduced before the last mixing zone.
- Extrusion and separation are carried out in such a way that a granulate of approximately 2.5-3 millimeters results, and so that expansion is prevented by low gas temperature, low pressure, and a large, unobstructed nozzle area (larger number of nozzle apertures).
- Extruder CM 45 Cincinnati Milcron Screw type: SK 400 Nozzle: 20 round apertures, 2.5 millimeters.
- the granulate obtained in this manner is conditioned to a total water content of 14%-wt by adjusting the air humidity, and in this state it is passed to an injection-molding machine for further processing.
- the injection molding machine is so operated that the entry section is kept cool (approximately 30 degrees Celsius) and the mass temperature does not exceed 165 degrees Celsius during the injection molding process.
- the injection molding mold is intensely cooled so that it does not exceed a temperature of 20 degrees Celsius even in the case of short cycle times.
- Expansion is prevented or suppressed by using greater injection entry cross-sections and smaller injection velocities in the first phase of the injection process.
- the properties of the mouldings so obtained are similar to those of wood and they can be finished by conventional wood-working methods such as drilling, sawing, sanding, slicing, cutting, gluing, dowelling, screwing, lacquering, coating, etc. Their resistance to corrosion is very similar to that of wood and for this reason it differs from such behavior as seen in the case of plastic.
- the surface hardness of the new mouldings obtained by using the above-described composition corresponds to that of commercially available hard PVC.
- Their workability corresponds to that of wood, although without the disadvantages displayed by thermo-plastifiable plastics, i.e., glazing and plugging of tools (sand paper, saws, files, drills, etc.).
- tools sand paper, saws, files, drills, etc.
- the amount of dust that is created during cutting operations is significantly less than is the case with wood or conventional wood-based materials.
- Example 2 In contrast to Example 1, all of the linseed oil is mixed into the recycled pulp at room temperature, with the rice meal being mixed in at the same time.
- the resin acid component (Sacocell 309 is a derivative of abietinic acid) in aqueous solution and with a solid content of 50%-wt is introduced just after the entry point; the glycerine is introduced at the middle. There is no introduction of a component just before the last mixing zone. In all other respects, work is carried out analogously to Example 1, and this also applies to process step 2.
- the granulate or pre-moldings obtained are not colored brown by the wood content. They can be colored as desired by the appropriate additives.
- Example 1 the cellulose fibers are coated with linseed oil; then the bone line and potato starch are mixed in and the dry mixture is placed into the extruder. Resin acid, glycol, and glutaraldehyde are introduced into the extruder housing at different points, the glutar aldehyde being added just before the last mixing zone, shortly before the extruder outlet.
- the pre-molding granulate obtained from process stage one was processed in the injection-molding machine under the conditions described for Example 1.
- the amount of linseed oil is unacceptably high when wood shavings are used as the fibre material, so that the separation of oil could be observed on the surface of the work pieces so obtained. It is obvious that, using this receipe, the upper limit for linseed oil had been exceeded.
- Sacotan 85 is a resin acid derivative with a low melting point.
- the glycerine used in this example is a crude glycerine from raps-methylester (rme) plants. Using this composition, once again, a higher proportion of wood fibre was tried with a simultaneously reduced quantity of starch. It was shown that both the manufacture of pre-molding granulate as well as the injection molding of the mouldings proceeded without any problems. An upper limit for the amount of wood in the end mixture was not nearly reached in this instance.
- the pre-moldings or pre-molding-granulate can be manufactured without any problem. However, the mechanical stability and strength of the mouldings that are obtained using this mixture are somewhat reduced.
- Example 2 In contrast to Example 2, the extrusion parameters used in the first stage of the process were modified in that the mass temperature was approximately 115 degrees Celsius. This brings about an improved disintegration of the starch components and, as a consequence of this, improved flow of the molding mass during injection molding during the second stage of the process. The expansion behavior was somewhat more difficult to manage when this was done.
- This mixture was selected in order to test the effects of a non-derivatised natural hard resin.
- the solid hard resin was added to the dry mixture in ground form.
- the granulates for the pre-molding can be produced without any problem. In contrast to this, separation from the mold at the injection molding machine varies from poor to unacceptable. There was also undesirable expansion. The lack of the oil component, in particular, clearly has a negative effect.
- the pre-mouldings-granulates obtained after the extrusion process are dried to a total water content of 5%-wt and then acted upon by the appropriate quantity of glycerine, this glycerine being completely resorbed by the granulate within a few hours.
- the mass can be processed at a temperature of 110-200 degrees Celsius, preferably, however, between 150-170 degrees Celsius.
- the injection mold was not cooled; rather, it was conditioned to a maximum of 90 degrees Celsius, preferably 80 degrees Celsius, when, because of the selected recipe and method of processing, problem-free separation from the mold nevertheless took place.
- the injection speed can be selected within a relatively wide range without any loss of quality, and compared to different injection speeds, the process proved to be stable and robust. However, it is recommended that a higher dwell pressure be set within the context of the closing force relationship in order to eliminate any partial expansion that may possibly occur during injection.
- Tempering to at most 90 degrees Celsius clearly has positive effects on the quality of the surface and the mechanical strength of the mouldings in comparison to those produced by according to the preceding examples.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Materials For Medical Uses (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Dental Preparations (AREA)
- Reinforced Plastic Materials (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Pens And Brushes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0151293A AT399883B (de) | 1993-07-29 | 1993-07-29 | Formkörper aus bzw. mit einem umweltverträglichen werkstoff, verfahren zu dessen herstellung sowie dessen verwendung |
| AT1512/93 | 1993-07-29 | ||
| PCT/EP1994/002535 WO1995004111A1 (fr) | 1993-07-29 | 1994-07-29 | Corps moule constitue par ou renfermant un materiau ne nuisant pas a l'environnement, son procede de fabrication et son application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5939192A true US5939192A (en) | 1999-08-17 |
Family
ID=3515302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/586,902 Expired - Fee Related US5939192A (en) | 1993-07-29 | 1994-07-29 | Moulding made from or including an environmentally acceptable material, a process for manufacturing the same, and the use of said moulding |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US5939192A (fr) |
| EP (1) | EP0712428B1 (fr) |
| JP (1) | JP3418400B2 (fr) |
| CN (1) | CN1098314C (fr) |
| AT (2) | AT399883B (fr) |
| AU (1) | AU7534094A (fr) |
| BR (1) | BR9407204A (fr) |
| CA (1) | CA2168221A1 (fr) |
| CZ (1) | CZ25096A3 (fr) |
| DE (1) | DE59405489D1 (fr) |
| DK (1) | DK0712428T3 (fr) |
| ES (1) | ES2115253T3 (fr) |
| HU (1) | HU219389B (fr) |
| PL (1) | PL181856B1 (fr) |
| RU (1) | RU2138526C1 (fr) |
| WO (1) | WO1995004111A1 (fr) |
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| US6296795B1 (en) | 2000-05-19 | 2001-10-02 | George S. Buck | Non-woven fibrous batts, shaped articles, fiber binders and related processes |
| EP1099368A3 (fr) * | 1999-11-10 | 2002-02-06 | Yasuo Iwamoto | Conteneur à plante et procédé de fabrication |
| US6488997B1 (en) * | 2000-03-31 | 2002-12-03 | Enviro Concept Ltd. | Degradable composite material, its disposable products and processing method thereof |
| WO2001068763A3 (fr) * | 2000-03-15 | 2003-05-15 | Apack Ag Bio Verpackungen | Revetement de corps moules biodegradables |
| FR2832348A1 (fr) * | 2001-11-16 | 2003-05-23 | Ralph Wicky | Formulation et procede de fabrication d'un recipient ou pot ou gobelet biodegradable |
| EP1321279A1 (fr) * | 2001-12-17 | 2003-06-25 | Wolfram Lihotzky-Vaupel | Procédé d'extrusion et produits pouvant être obtenus à l'aide de ce procédé |
| EP1321264A1 (fr) * | 2001-12-17 | 2003-06-25 | Wolfram Lihotzky-Vaupel | Procédé de production de granulés |
| WO2003051613A1 (fr) * | 2001-12-17 | 2003-06-26 | Hb-Feinmechanik Gmbh Co Kg | Procede de production de corps façonnes |
| US20040092613A1 (en) * | 2000-08-14 | 2004-05-13 | Errington John Gough | Method for the production of biodegradable foamed products |
| WO2004104106A1 (fr) * | 2003-05-20 | 2004-12-02 | Ralph Wicky | Formulation et procede de fabrication d'un recipient ou pot ou godet biodegradable |
| WO2006038245A1 (fr) * | 2004-10-08 | 2006-04-13 | Acroplastica S.R.L. | Procede de fabrication de planches pour recouvrir des panneaux superieurs d'appareils electromenagers et planches obtenues selon de procede |
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| WO2006105629A1 (fr) * | 2005-04-06 | 2006-10-12 | Phb Industrial S.A. | Récipient de semis, méthode pour produire un récipient de semis et méthode de croissance et de plantation de semis |
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| CN103665633B (zh) * | 2013-11-01 | 2016-03-23 | 界首市佳通塑胶制品有限公司 | 一种发泡型环保木塑复合材料 |
| US20210213680A1 (en) * | 2017-11-10 | 2021-07-15 | Singapore University Of Technology And Design | An apparatus for large scale additive manufacturing, and a material for manufacturing |
| US11820077B2 (en) * | 2017-11-10 | 2023-11-21 | Singapore University Of Technology And Design | Apparatus for large scale additive manufacturing, and a material for manufacturing |
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| WO2021224881A1 (fr) * | 2020-05-08 | 2021-11-11 | Greentech Global Pte. Ltd. | Procédés de dérivation d'origine biologique de matériaux cellulosiques et synthétiques et articles obtenus à partir de ceux-ci |
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2115253T3 (es) | 1998-06-16 |
| PL312791A1 (en) | 1996-05-13 |
| HU9600190D0 (en) | 1996-03-28 |
| BR9407204A (pt) | 1996-09-17 |
| HU219389B (en) | 2001-03-28 |
| RU2138526C1 (ru) | 1999-09-27 |
| EP0712428B1 (fr) | 1998-03-18 |
| JP3418400B2 (ja) | 2003-06-23 |
| HUT73824A (en) | 1996-09-30 |
| DE59405489D1 (de) | 1998-04-23 |
| ATA151293A (de) | 1994-12-15 |
| DK0712428T3 (da) | 1998-12-28 |
| CN1131957A (zh) | 1996-09-25 |
| AT399883B (de) | 1995-08-25 |
| CA2168221A1 (fr) | 1995-02-09 |
| ATE164179T1 (de) | 1998-04-15 |
| EP0712428A1 (fr) | 1996-05-22 |
| JPH09500924A (ja) | 1997-01-28 |
| PL181856B1 (pl) | 2001-09-28 |
| CZ25096A3 (en) | 1996-06-12 |
| WO1995004111A1 (fr) | 1995-02-09 |
| CN1098314C (zh) | 2003-01-08 |
| AU7534094A (en) | 1995-02-28 |
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